Salty Matters

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Evaporite interactions with magma Part 2 of 3: Nature of volatile exhalations from saline giants?

John Warren - Saturday, March 16, 2019



This article discusses general mechanisms of earth-scale volatile entry into the ancient atmosphere during events that involved rapid and widespread heating of saline giants. It develops this notion by looking at whether volumes of volatiles escaping to the atmosphere are enhanced by either the introduction of vast quantities of molten material to a saline giant or the thermal disturbance of that salt basin by bolide impacts. This begins a discussion of the contribution of heated evaporites in two (or three if the Captitanian is counted as a separate event) of the world's five most significant extinction events. It also looks at possible evaporite associations with a substantial bolide impact that marks the end of the Cretaceous. The next article presents the geological details and implications of the various magma-evaporite-volatile associations tied to major extinction events.

As we have seen for evaporite interactions with giant and supergiant volumes of commodities in particular deposits, such as hydrocarbons, base metals (Cu, Pb-Zn and IOCG deposits) evaporites do not form a commodity accumulation. But if evaporites are involved in the accumulation and enrichment processes, the size and strength of the accumulation are much improved. Because of their high reactivity compared to the kinetic stability at and near  thelithosphere's surface across most other lithologies, evaporite act not as creators of enrichment but as facilitators of enrichment (Warren, 2016 Chapters 9, 10, 14, 15 and Salty Matters, March 31, 2017).

End-Permian event

The end-Permian extinction event, colloquially known as the Great Dying, occurred around 252 Ma (million years) ago, and defines the boundary between the Permian and Triassic geologic periods, as well as between the Palaeozoic and Mesozoic eras. It is the Earth's most severe extinction event, when up to 96% of all marine species, 70% of terrestrial vertebrate species disappeared (Table 1, Figure 1). It also involves the only known mass extinction of a number of insect species (≈25%). Some 57% of all biological families and 83% of all genera became extinct. The end-Cretaceous extinction, which marks the demise of dinosaurs, is less severe, although it probably has a stronger hold on the western zeitgeist, while on land, the end-Triassic event marks the ascendancy of the dinosaurs.

Suggested mechanisms driving the end-Permian extinction event include; massive volcanism centred on the Emeishan and Siberian Traps and the ensuing coal or gas fires and explosions, along with a runaway greenhouse effect that was triggered by temperature increases in marine waters (Figure 2). It also may have involved one or more large meteor impact events and a rise in oceanic water temperatures that drove a sudden release of methane from the sea floor due to methane-clathrate dissociation.

The end-Permian event follows on closely from the Capitanian (Emeishan) extinction event when in south China fusulinacean foraminifers and brachiopods lost 82% and 87% of species, respectively (Bond et al., 2015). Proximity in time of the two events may explain why the breadth of the end-Permian extinction event was so severe. The Earth's biota was still recovering from the Emeishan event when the vicissitudes of the End-Permian calamity further decimated the world's biota.

Both the Emeishan and end-Permian extinction events tie to elevated mercury levels in sediments that encompass their respective boundaries (Grasby et al., 2016). Astride both boundaries, the mercury stratigraphy shows relatively constant background values of 0.005–0.010 μg g–1. However, there are notable spikes in Hg concentration over an order of magnitude above background associated with the two extinction events. The Hg/total organic carbon (TOC) ratio shows similar large spikes, indicating that they represent a real increase in Hg loading to the environment. These Hg loading events are associated with enhanced Hg emissions created by the outflows of the Emeishan and end-Permian large igneous province (LIP) magmas.

Interestingly, there is indirect evidence for a synchronous antipodeal impact crater that some argue may have instigated the Siberian volcanism, in much the same way that the end-Cretaceous bolide impact on the Yucatan Peninsula is considered by some to be the antipodeal driver of the Deccan Trap volcanism (von Frese et al., 2009). Other contributing, but likely more gradual tiebacks to the Great Dying, include sea-level variations, increasing oceanic anoxia, increasing aridity tied to the accretion of the Pangean supercontinent, and shifts in ocean circulation driven by climate change (Figure 2).

End-Triassic event

The end-Triassic extinction event, some 201.3 Ma, defines the Triassic-Jurassic boundary. In the oceans, a whole class (conodonts) and 23-34% of marine genera disappeared. On land, all archosaurs other than crocodylomorphs (Sphenosuchia and Crocodyliformes) and Avemetatarsalia (pterosaurs and dinosaurs), some remaining therapsids, and many of the large amphibians became extinct. About 42% of all terrestrial tetrapods went extinct (Figure 3). This event vacated terrestrial ecological niches, allowing the dinosaurs to assume the dominant roles in the Jurassic period. It happened in less than 10,000 years and occurred just before the Pangaean supercontinent started to break apart (Tanner, 2018).

The extinction event marks a floral turnover as well. About 60% of the diverse monosaccate and bisaccate pollen assemblages disappear at the T-J boundary, indicating a significant extinction of plant genera. Early Jurassic pollen assemblages are dominated by Corollina, a new genus that took advantage of the empty niches left by the extinction.

Worldwide the end-Triassic extinction horizon is marked by perturbations in ocean and atmosphere geochemistry, including the global carbon cycle, as expressed by significant fluctuations in carbon isotope ratios (Korte et al., 2019). At this time the Central Atlantic Magmatic Province (CAMP) volcanism triggered environmental changes and likely played a crucial role in this biotic crisis (Schoene et al., 2010). Biostratigraphic and chronostratigraphic studies link the end-Triassic mass extinction with the early phases of CAMP volcanism, and notable mercury enrichments in geographically distributed marine and continental strata are shown to be coeval with the onset of the extrusive emplacement of CAMP (Percival et al. 2017; Marzoli et al., 2018). Sulphuric acid induced atmospheric aerosol clouds from subaerial CAMP volcanism can explain a brief, relatively cool seawater temperature pulse in the mid-paleolatitude Pan-European seaway across the T–J transition. The occurrence of CAMP-induced carbon degassing may explain the overall longterm shift toward much warmer conditions.

End-Cretaceous event

The end-Cretaceous extinction event defines Cretaceous-Tertiary (K–T) boundary, and was a sudden mass extinction event some 66 million years ago. Except for some ectothermic species, such as the leatherback sea turtle and crocodiles, no tetrapods weighing more than 25 kilograms survived. The K-T event marked the end of the Cretaceous period and with it, the entire Mesozoic Era, opening the Cenozoic Era.

A wide range of species perished in the K–T extinction, the best-known being the non-avian dinosaurs. It also destroyed a plethora of other terrestrial organisms, including certain mammals, all pterosaurs, some birds, lizards, insects, and plants. In the oceans, the extinction event killed off plesiosaurs and the giant marine lizards (Mosasauridae) as well as devastating fish, sharks, molluscs (especially ammonites, which became extinct) populations, and many species of plankton. It is estimated that 75% or more of all species on Earth vanished in the end-Cretaceous event.

In its wake, the same extinction event also provided evolutionary opportunities as many groups underwent remarkable adaptive radiation—sudden and prolific divergence into new forms and species within the disrupted and emptied ecological niches. Mammals in particular diversified in the Paleogene, evolving new forms such as horses, whales, bats, and primates. Birds, fish, and perhaps lizards also radiated in newly vacant niches.

In the geologic record, the K–T event is marked by a thin layer of sediment called the K–Pg (Cretaceous - Paleogene) boundary, that is found throughout the world in both marine and terrestrial rocks. The boundary clay shows high levels of the metal iridium and is widely interpreted as indicating the impact of a massive comet or asteroid 10 to 15 km (6 to 9 mi) wide some 66 million years ago (Figure 4a,b). The impact devastated the global environment, mainly through a lingering impact winter, which halted photosynthesis in plants and plankton.

The impact hypothesis, also known as the Alvarez hypothesis (Alvarez et al., 1980), was bolstered by the discovery of the 180-kilometer-wide (112 mi) Chicxulub crater in the Gulf of Mexico in the early 1990s, which provided conclusive evidence that the K–Pg boundary clay represented debris from an asteroid impact. In a 2013 paper, Paul Renne dated the impact at 66.043±0.011 million years ago, based on argon-argon dating (Renne, 2013). He went on to conclude that the main end-Cretaceous mass extinction event occurred within 32,000 years of this date. A 2016 drilling project into the Chicxulub peak ring, confirmed that the peak ring was comprised of granite, likely ejected within minutes from deep in the earth, but the well contained hardly any anhydrite/gypsum, the usual sulphate-containing seafloor rock across the region (Figure 4a, b). As we shall see in part 3, the missing CaSO4 was vaporised in the impact and dispersed as sulphurous aerosols into the atmosphere, causing longer-term deleterious effects on the climate and food chain. Another causal or contributing factors to the end-Cretaceous extinction event may have been the synchronous outflows of the Deccan Traps and other volcanic eruptions, so driving climate change, and possibly sea level change (von Frese et al., 2009).

Volatiles released when cooking saline giants and associated organic-rich sediments

Particular sets of assimilations and metamorphic alterations of evaporites occur within the explosive milieu associated with both igneous interactions and pressurised heating of salts tied to a bolide impact. Any carbonate and organic matter layers present in the saline sequence or adjacent strata generates additional volatiles that will quickly enter the earth's atmosphere. Figure 5 is a schematic of the estimated amount of volatiles released during contact metamorphism of different types of sedimentary rocks in contact with an igneous sill or magma body (after Ganino et al., 2009; Pang et al., 2013). More catastrophic volumes of similar volatile suites enter the atmosphere if a large bolide impacts a region underlain by a saline giant.

Hence, salty interactions must be considered and quantified when attempting to understand earth-scale environmental changes whenever large evaporite masses are caught up in regions of LIP emplacement or bolide impact. In such areas:

  • Basalt and granitoids do not release large volumes of volatiles, as compared to the amounts of volatiles that are released by the heating or assimilation of saliniferous country rock (heat transfer and hydrothermal circulation).
  • Most porous sandstones and organic-lean shales caught up in a contact aureole or consumed in a magma, release water vapour; a release that has little effect on global climate.
  • During desulphation of a magma, gypsum or anhydrite masses are assimilated into a rising magma chamber or the emplacement of a thick sill. If anhydrite beds are consumed (melted and absorbed) by a magma batholith, the reaction releases abundant SO2 constituting up to 47 wt% of the bedded sulphate (Gorman et al., 1984). Direct melting requires high temperatures (≈ 1300- 1400 °C). Such widespread desulphation of thick Devonian anhydrite beds occurred during the emplacement of the supergiant Noril'sk nickel deposit in Siberia (Black et al., 2014; Warren, 2016, Chapter 16).
  • But such elevated temperatures (≈1400°C) are not typical of most contact aureoles where a sill or dyke intrudes anhydritic country rock. However, similar high-volume SO2 releases can proceed at temperatures as low as 615°C if the anhydrite is impure and contains interlayers rich in organics and hydrocarbons (e.g., West and Sutton, 1954; Pang et al., 2013). This is especially so if the interacting calcium sulphate is gypsum (hydrated salt) rather than anhydrite. Experiments by Newton and Manning (2005) demonstrated that the solubility of anhydrite increases enormously with NaCl activity (salinity) in hydrothermal solutions at ≈600 to 800°C (Figure 6).

  • Pure limestone contains large amounts of CO2, but like anhydrite the thermal decomposition of limestone or dolomite into CaO, MgO and CO2 takes place at high temperatures (>950 °C) that are typical when blocks of sedimentary carbonate are assimilated into a magma chamber, but less typical of contact aureoles tied to dykes and sills. Impure limestones can release large amounts of CO2 (up to 29 wt%) during the formation of calc-silicates in the contact aureole at moderate temperatures of 450–500 °C. As early as 1940, Bowen documented the release of CO2 by decarbonisation reactions during progressive metamorphism of siliceous dolomites (Bowen, 1940)
  • Likewise, devolatilization of fine-grained calcareous and saline sedimentary rocks during contact metamorphism directly generates fluids rich in CO2 (i.e., decarbonisation) and SO2 (i.e., desulphatation), which in theory can enter the magmatic system.
  • When heated at a relatively low temperature (<300-400 °C), contact metamorphism and hydrothermal leaching of bituminous halite and organic-carbon-rich saline mudstones releases large volumes of chlorohalogens and methane (Visscher et al., 2004; Beerling et al., 2007). Halocarbon compounds (aka halogenated hydrocarbons) are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine or iodine). Methyl chloride (CH3Cl) and methyl bromide (CH3Br) are commonplace halocarbons when a halite-dominant saline giant interacts with igneous sill emplacement. When thermally-derived chlorohalogens enter the upper atmosphere, they tend to be reactive and will degrade ozone.
  • Buring coal and coal gas release abundant CO2. Depending on its grade, coal can ignite at temperatures between 400-530°C. Methane will auto-ignite at temperatures around 550-600°C and in an oxygenated setting produces large volumes of carbon dioxide and water vapour. Flashpoints are much lower than these ignition temperatures.
  • Sulphidic (pyritic) sediments release abundant SO2 when heated at lower temperatures (<400°C).
  • Heating of hydrated salts at moderate temperatures (90-250°C) can release pressurised pulses of hypersaline chloride or sulphate brine, with the dominant ionic proportions dependent on predominant hydrated salt; e.g., carnallite incongruently alters as it releases an MgCl2 brine, gypsum incongruently alters as it releases a Ca-SO4 brine (see part 1). Such pressurised pulses are essential in the generation of explosive breccia pipes sourced at the sill penetration level in the hydrated evaporite interval (discussed in detail for the Siberian Traps in part 3).
  • Getting volatiles into the atmosphere

    When a saline giant is heated during emplacement of a large igneous province (LIP) or during the impact of a large bolide, it and adjacent carbonates and organic-rich mudstones release large volumes of volatiles that can have short and long term harmful effects on the Earth's biosystems (Black et al., 2012, 2014; Jones et al., 2016; Part 3 this series). The volume of volatiles released to the atmosphere by these interactions, especially sulphurous products (SO2, H2S), thermogenic CH4, organohalogens and CO2, are considered primary contributors to three or four of the major extinction events outlined in Figure 1, and perhaps others, as discussed in part 3.

    Height and volume of various volatile injections into the layers of Earth's atmosphere controls the longevity and intensity of climatic effects and are tied to the chemistry of particular volatiles (Figure 7; Textor et al., 2003; Robock, 2000). The low concentration of water in typical modern volcanic plumes results in the formation of relatively dry aggregates entering the atmosphere. More than 99% of these aggregates are frozen because of their fast ascent to low-temperature regions of the atmosphere. With increased salinities, the salinity effect increases the amount of liquid water attaining the stratosphere by one order of magnitude, but the ice phase is still highly dominant. Consequently, the scavenging efficiency for HCl is very low, and only 1% is dissolved in liquid water.

    Scavenging by ice particles via direct gas incorporation during diffusional growth is a significant process for volatile transport. The salinity effect increases the total scavenging efficiency for HCl from about 50% to about 90%. The sulfur-containing gases SO2 and H2S are only slightly soluble in liquid water; however, these gases are incorporated into ice particles in the atmosphere with an efficiency of 10 to 30%. Despite scavenging, more than 25% of the HCl and 80% of the sulphur gases reach the stratosphere during a more intense modern explosive eruption because most of the particles containing these species are typically lifted there by the force of the eruption (Figure 7b).

    Sedimentation of the particles tends to remove the volcanic gases from the stratosphere. Hence, the final quantity of volcanic gases injected in a particular eruption depends on the fate of the particles containing them, which is in turn dependent on the volcanic eruption intensity and environmental conditions at the site of the eruption.

    Today, volcanically-derived SO2 and H2S are the dominant sources for sulphur species in the atmosphere (Jones et al., 2016; Robock, 2000). Conversion of SO2 to aerosols is one of the critical drivers of climatic cooling during recent eruptions (Figure 7a; Robock, 2000). For SO2 to be effective in causing cooling in the atmosphere, escaping hydrogen sulphide quickly oxidises to SO2. Over hours to weeks following its eruptive escape the ongoing reaction of SO2 with atmospheric H2O forms a H2SO4 (sulphuric acid) aerosol, and this is a major cause of the acid rains tied to volcanism (Figure 7a, b).

    Tropospheric sulphate aerosols have an atmospheric lifetime of a couple of weeks due to the rapid incorporation as precipitation into the hydrological cycle (Figure 7b; Robock, 2000). However, if the intensity of the escaping volatile plume is capable of injecting sulphurous material above the tropopause into the stratosphere, then due to the lack of removal by precipitation, the lifetimes of sulphurous aerosols and the associated cooling effects are considerably extended (years rather than weeks: Figure 7a versus 7b).

    Modern eruptions

    World-scale cooling has been observed following a number of modest (by large igneous province standards) volcanic eruptions over the past few centuries (Figure 8; Bond and Wignall, 2014; Sigurdsson, 1990; and references therein). A recent example is provided by the Mount Pinatubo eruption of 1991, which injected 20 megatons of SO2 more than 30 km into the stratosphere. The result was a global temperature decrease approaching 0.5 °C for three years (although this cooling was probably exacerbated contemporaneous Mount Hudson eruption in Chile). One of the largest historical eruptions occurred in 1783-1784 from the Laki fissure in Iceland when a ≈15 km3 volume of basaltic magma was extruded, releasing ≈122 Mt of SO2, 15 Mt of HF, and 7 Mt of HCl. Laki’s eruption columns extended vertically up to 13 km, injecting sulfate aerosols into the upper troposphere and lower stratosphere, where they reacted with atmospheric moisture to produce ≈200 Mt of H2SO4. This aerosol-rich fog hung over the Northern Hemisphere for five months, leading to short-term cooling, and harmful acid rain in both Europe and North America. Additionally, HCl and HF emissions damaged terrestrial life in Iceland and mainland Europe, as this low-level fluorine-rich haze stunted plant growth and acidified soils.

    By causing or aiding in the collapse of food chains during the more intense sulphurous releases involved in the heating of large volumes of anhydrite held in ancient saline giants, vast quantities of acid rain may have killed much of the vegetation on land and photosynthetic organisms in the oceans during the three extinction events discussed in part 3.


    For halocarbons to form in a volcanic eruption requires the combination halogens with organic matter/methane or other hydrocarbons. We shall consider the levels and origins of two of the more common halocarbons in today's atmosphere; methyl chloride (CH3Cl) and methyl bromide (CH3Br) although many other species of halogenated hydrocarbons are present both naturally and anthropogenically (Schwandner, 2002; Visscher et al., 2004).

    The average Cl concentration of the Earth has been estimated to be 17 ppm (Worden, 2018 and references therein). Chlorine is the dominant anion in seawater, most modern and ancient evaporite beds and associated brines. Chlorine is present in most igneous rocks at low concentrations with little difference in level shown between granite and basic igneous rocks (both have a Cl- concentration of about 0.02%). However, igneous glass typically has higher Cl concentrations (≈0.08%). Chlorine is concentrated within any residual vapour phase during volcanic eruptions so can be independent of the volatiles created by heating of saline giants. Without the latter, the contribution of volcanically-erupted Cl to the atmosphere is still considerable. For example, the estimated current global volcanic emission of Cl is between 0.4 and 170 mt/year, while individual eruptions can produce hundreds of kilotons of Cl. For example, in 1980, St Helens emitted 670 kt of Cl into the atmosphere.

    In crystalline igneous rocks Br is found at low concentrations, typically <1 ppm in mid-ocean ridge basalts (MORB) (Worden, 2008 and references)). The average Br concentration of the Earth has been estimated to be 0.05 ppm. Chlorine/Bromine ratios are typically between 200 and 1000 in igneous rocks. Bromine is, however, found at relatively high concentrations (up to 300 ppm) in melt inclusions and matrix glass in acid igneous rocks since it is a highly incompatible element that does not easily sit within silicate, oxide or sulphide minerals. Bromine is concentrated within any residual vapour phase during volcanic eruptions. Based on experimentally-derived fractionation factors for halogens in volcanic materials, crustal average halogen concentrations, and measured amounts of Cl emitted from volcanoes, it can be concluded that the contribution of volcanically-erupted Br to the atmosphere is considerable. For example, the estimated current global volcanic emission of Br is between 2.6 and 78 kt while individual eruptions (e.g., St Helens in 1980) can emit 2.4–5.6 kt.

    The hinterlands of sedimentary basins that predominantly enriched in primary igneous rocks will provide only small quantities of Br into the sediment supply but rocks enriched in glass-bearing igneous rocks may supply relatively greater amounts of Br (Worden, 2018). Bromine is found in sedimentary basins as dissolved Br-, in solid solution in halite (NaClxBr1−x), or in less common salts resulting from potash-facies evaporites, such as sylvite. Bromine is also associated with organic-rich sediments, especially in marine settings, including organic-rich mudstone and coal. At a concentration of 65 mg/L, Br- is the second most abundant halogen in modern seawater.

    Organic matter and its more evolved forms –kerogen and hydrocarbons– are typical of most large evaporite basins. Mesohaline carbonates interlayered with anhydrite and halite beds can entrain high levels of organic matter to form high-yield source rocks, while the brine inclusions in some halites contain high amounts of volatile hydrocarbons and pyrobitumens. Evaporite beds composed of anhydrite or halite make excellent seals holding back large volumes of hydrocarbons (for literature documentation of these observations see Warren, 2016, Chapters 9 and 10). In combination, saline giants and their heat-responsive lithologies will contain vast volumes of potential volatiles, including halocarbons.

    Ozone (O3) destruction

    When halocarbons enter the stratosphere, they decimate the ozone layer, allowing harmful levels of ultraviolet (UV) radiation to reach the earth's surface (Figures 7a, 9a). Ozone is destroyed by the entry of a number of free radical catalysts into the stratosphere; today the most important catalysts are the hydroxyl radical (OH), nitric oxide radical (NO), chlorine radical (Cl) and the bromine radical (Br). Each radical is characterised by an unpaired electron in its molecular structure and is thus extremely reactive. All of these radicals have both natural and man-made sources; at present, most of the OH and NO in the stratosphere is naturally occurring, but human activity has drastically increased the levels of chlorine and bromine.

    The elements that form radicals in the stratosphere are found in stable organic compounds, especially halocarbons, which reach the stratosphere without being destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl and Br atoms are released from the parent halocarbon by the action of ultraviolet light.

    Ozone (O3) is a highly reactive molecule that quickly reduces to the more stable oxygen (O2) form with the assistance of a catalyst (radical). Cl and Br atoms destroy ozone molecules through a variety of catalytic cycles. The simplest example of such a reaction is when a chlorine atom reacts with an ozone molecule, taking an oxygen atom to form chlorine monoxide (ClO) and leaving behind an oxygen molecule (O2) (Figure 9b). The ClO can then react with another molecule of ozone, once more releasing the chlorine atom as ClO, so far yielding two molecules of oxygen. This ClO reaction can be repeated until the ClO is flushed from the stratosphere (Figure 9b, Fahey, 2007)

    Thus the overall effect of halocarbons entering the stratosphere is a decrease in the amount of ozone. A single chlorine radical can continuously destroy ozone for up to two years (this the time scale for its transport back down into the troposphere; Figure 7a). But there are other stratopheric reactions that remove CLO from this catalytic cycle by forming reservoir species such as hydrogen chloride (HCl) and chlorine nitrate (ClONO).

    Bromine radicals are even more efficient than chlorine at destroying ozone on a per-atom basis, but at present there is much less bromine than chlorine in the atmosphere. Laboratory studies have shown that fluorine and iodine atoms can participate in similar catalytic cycles. However, fluorine atoms react rapidly with water and methane to form strongly bound HF in the Earth's stratosphere, while organic molecules containing iodine react so quickly in the lower atmosphere that they do not reach the stratosphere in significant quantities.

    Halocarbon concentrations below the tropopause are always higher by several orders of magnitude than in the stratosphere, which contains the seasonally and locally variable ozone layer responsible for absorption of incident solar UV radiation (Schwandner, 2002). Penetration of the tropopause allows the ascent of long-lived halocarbons and today occurs primarily as a result of rising tropical air masses in a Hadley cell, rare turnover events, or large Plinian volcanic eruptions.

    Over the two to three years a chlorine or bromine radical can remain in the stratosphere, it reacts with ozone and converts it to oxygen. It has been estimated that a single chlorine atom can react with an average of 100,000 ozone molecules before it is removed from the catalytic cycle (Figure 8b. Other halocarbon-enabled reactions drive ozone destruction (these catalysts are derived from anthropogenic CFCs and other industrial halocarbons). Over the past half-century, our anthropogenic focus on ozone destruction from industrial chemicals has driven the public's understanding into to the much-needed legislated prevention of the entry of additional industrial halocarbons (especially CFCs) into the stratosphere.


    However, there are additional deep-time implications for the health of the Earth's biota when natural events of the past drastically increased the amount of halocarbons entering the stratosphere, along with increased levels of sulphurous volatiles and greenhouse gases. We know modern volcanic exhalations containing relatively high levels of chlorine and bromine. But times of intense magmatic/volcanogenic or bolide heating of evaporites in a saline giant will contribute even greater volumes of halocarbons to the stratospheric levels of the atmosphere (Figure 10). If coals and peats are also present (typically not in the saline portion of the basin's sediment fill), then the heating of these additional organic-rich sediments will contribute even more carbon to the vast volumes of the halocarbons created by heating of the evaporites. Heating reactions in the saline giant and associated deposits can also supply elevated levels of the greenhouse gases CO2 and CH4. Explosive volcanism tied to the emplacement of LIPs in the region of a saline giant or the atmosphere-scale disturbance linked to the impact of a large bolide in an area underlain by a saline giant are efficient mechanisms to move large volumes of halocarbons, sulphurous volatiles and greenhouse gasses to the troposphere. The third article in this series will document the specific evaporite geology that contributed to four of the five major Phanerozoic extinction events (Figure 10).


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    Salt Dissolution (3 of 5): Natural Geohazards

    John Warren - Tuesday, October 31, 2017


    Surface constructions and other anthropogenic activities atop or within evaporite karst terranes is more problematic than in subcopping carbonate terranes due to inherently higher rates of dissolution and stoping (Yilmaz et al., 2011; Cooper and Gutiérrez, 2013; Gutiérrez et al., 2014). Overburden collapse into nearsurface gypsum caves can create stoping chimneys, which break out at the surface as steep-sided dolines, often surrounded by broader subsidence hollows. Such swallow-holes, up to 20 m deep and 40 m wide, continue to appear suddenly and naturally in gypsum areas throughout the world.

    Unlike the relatively slow formation of limestone karst, gypsum/halite karst develops on a human/engineering time-scale and can be enhanced by human activities (Warren, 2016, 2017). For example, in 2006, the Nanjing Gypsum mine in China broke into a phreatic cavity in a region of gypsum karst, driving complete flooding of the mine in some three days. Associated groundwater drainage caused a sharp drop in the local piezometric level of up to 90 m in a well in nearby Huashu village. Resultant ground subsidence severely damaged nearby roads and buildings (Wang et al., 2008). In Ukraine, dewatering of gypsum karst to facilitate sulphur mining substantially increased the rate of gypsum dissolution and favoured the expansion of sinkholes within an area affected by the associated cones of water-table depression (Sprynskyy et al., 2009). Natural evaporite karst enhanced by intrastructure focusing of drainage creates the various scales of problem across the Gypsum Plain of West Texas and New Mexico (Stafford et al., 2017).

    Although halite is even more susceptible to rapid dissolution than gypsum, it typically is not a major urban engineering problem; large numbers of people simply do not like to live in a climate that allows halite to make it to the surface. However, in the Dead Sea region, the ongoing lowering of the water level encouraged karstic collapse in newly exposed mudflats and has damaged roads and other man-made structures (Frumkin et al. 2011; Shviro et al., 2017). Catastrophic doline collapse atop poorly managed halite/potash mines and solution brine fields is an additional anthropogenically-induced or enhanced geohazard in developed regions is discussed in detail in Warren, 2016 (Figure 1).

    Gypsum karst is a documented natural hazard in many parts of Europe (Figure 2), and similar areas of shallow subcropping gypsum are common in much of the rest of the world (Table 1). For example, areas surrounding the city of Zaragoza in northern Spain are affected, as is the town of Calatayud (Gutiérrez and Cooper, 2002; Gutiérrez, 2014). Gypsum dissolution is responsible for subsidence and collapse in many urban areas around northern Paris, France (Toulemont, 1984), in urban areas in and around Stuttgart and other towns peripheral to the Harz Mountains in Germany (Garleff et al., 1997), in Pasvalys and Birzai in Lithuania (Paukstys et al., 1999), in the Muttenz-Pratteln area in northwestern Switzerland (Zechner et al., 2011), in the Perm area of Russia (Trzhtsinsky, 2002), in the Sivaz region of Turkey (Karacan and Yilmez, 1997), in the region centred on the city of Mosul in northern Iraq (Jassim et al., 1997) and in a number of areas of rapid urban development in eastern Saudi Arabia (Amin and Bankher, 1997a, b). Large subsidence depressions caused by gypsum dissolution in China have opened up in the Taiyuan and Yangquan regions of Shanxi Coalfield and the adjacent Hebei Coalfield.

    Variation in the watertable level, induced by groundwater pumping or uncontrolled brine extraction, can be an anthropogenic trigger for dolines surfacing. As the watertable declines it causes a loss of buoyant support to the ground, it also increases the flow gradient and water velocity, which facilitates higher rates of crossflow and deeper aquifer recharge in subsequent floods and so reduces the geomechanical strength of the cover and washes away roof span support (Figures 1, 3). Dolines can also be associated with groundwater quality issues. Collapse dolines or sinkholes are frequently used as areas or sumps for uncontrolled dumping industrial and domestic waste. Because of the direct connection between them and the regional aquifer, uncontrolled dumping can cause rapid dispersion of chemical and bacterial pollutants in the groundwater. In the case of Riyadh region Saudi Arabia, a lake of near-raw sewage has appeared in Hit Dahl (cave) and is likely related to the increased utilisation of desalinated water for sanitation and agriculture (Warren, 2016). In the Birzai region of Lithuania numerous sinkholes developed in Devonian gypsum subcrop are in direct connection across the regional hydrology. Accordingly, the amount of agricultural fertilizer use is limited to help protect groundwater quality.

    One of the problems associated with rapid surfacing of evaporite collapse features is that any assignment of sinkhole cause will typically lead to an assignment of blame, particulary when anthropogenic infrastructure has been damaged or destroyed by the collapse, or lives may have been lost. Areas of natural evaporite karst are typically areas of relatively shallow evaporites. Shallow evaporites make such regions suitable for extraction via conventional or solution mining. When a collapse does occur in a mined area, one group (generally the miners) has a vested interest in arguing for natural collapse, the others, generally the lawyers and their litigants, will argue for an anthropogenic cause. The reality is usually a combination of natural process enhanced to varying degrees by human endeavours. In the examples in this section, much of the driving process for the collapse is natural, while the cause of any unexpected karst-related disaster is typically geological ignorance combined with political/community intransigence. See Chapter 13 for a further discussion of karst and stope examples that include collapses and explosions where the anthropogenic drivers can dominate.

    Problems in the Ripon area, Yorkshire, UK

    The town of Ripon, North Yorkshire, and town’s surrounds experiences the worst ongoing gypsum-karst related subsidence in England (Figures 3, 4; Cooper and Waltham, 1999). Some 43 events of subsidence or collapse in the caprock over the Ripon gypsum have occurred over the last 160 years, within an area of 7 km2 (Figures 4). This gives a mean rate of one new sinkhole every 26 years in each square kilometre. Worldwide, the highest documented event rate occurs in Ukraine, in an area of thin and weak clay caprocks above interstratal gypsum karst, where new sinkholes appear at a rate of 0.01 to 3.0 per year per km2 (Waltham et al., 2005). In the Ripon area, numerous sags and small collapses also typify surrounding farmlands. Subsidence features are typically 10-30m in diameter, reach up to 20m in depth and can appear at the surface in a matter of hours to days (Figure 3). To the east of the town, one collapse sinkhole in the Sherwood Sandstone is 80 m in diameter and 30 m deep, perhaps reflecting the stronger roof beam capacity of the Sherwood Sandstone.

    When a chimney breaks through, the associated surface collapse is very rapid (Figure 3 b-e). For example, one such subsidence crater, which opened up in front of a house on Ure Bank terrace on 23rd and 24th April, 1997, is documented by Cooper (1998.) as follows (Figure 3b).

    “...The hole grew in size and migrated towards the house, to measure 10m in diameter and 5.5m deep by the end of Thursday. Four garages have been destroyed by the subsidence. This collapse was the largest of one of a series that have affected this site for more than 30 years; an earlier collapse had demolished two garages on the same site, and a 1856 Ordnance Survey map shows a pond on the same site. The hole is cylindrical but will ultimately fail to become a larger, but conical, depression. As it does so, it may cause collapse of the house, which is already damaged, and the adjacent road. The house and several nearby properties have been evacuated and the nearby road has been closed. The gas and other services, which run close to the hole, have also been disconnected in case of further collapse.”

    Cooper (1998) found the sites of most severe subsidence in the Ripon area (including the house at Ure Terrace and in the vicinity of Magdelen's Road) are located at the sides of the buried Ure Valley, an area where the significant volumes of water seeps from the gypsum karst levels into the river gravels (Figure 4). In 1999 the Ure Terrace sinkhole was filled using a long conveyor belt that was cantilevered over the hole so that no trucked needed to back up close to the sinkhole opening. The hole was surcharged to a height of 0.5m. The hole remains unstable, but the collapse of the fill is monitored to document fill performance and the fill is periodically topped up. After the sinkhole was filled, the road adjacent to the sinkhole was re-opened and the site of the sinkhole fenced. The severely damaged Field View house remains standing next to the sinkhole. The nearby Victorian Ure lodge was not directly damaged by the 1997 sinkhole, but its western corner fell within the council-designated damage zone, and was left unoccupied. It fell into disrepair and was subsequently demolished (Figure 3b). A similar fate befell houses damaged by the surfacing of collapse sinkholes in and around Magdelen's Road, which is located a few hundred metres from Ure Terrace (Figure 3c-e). Shallow subcropping Zechstein gypsum (rehydrated anhydrite) occurs in two subcropping bedded units in this area, one is in the Permian Edlington and the other is in the Roxby Formation (Figure 4b). Together they form a subcrop belt about a kilometre wide, bound to the west by the base of the lowest gypsum unit (at the bottom of the Edlington Formation) and to the east by a downdip transition from gypsum to anhydrite in the upper gypsum-bearing unit of the Roxby Formation. The spatial distribution of subsidence features within this belt relates to joint azimuths in the Permian bedrock, with gypsum maze caves and subsidence patterns following the joint trends (Cooper, 1986). Most of the subcropping gypsum is alabastrine in the area around Ripon, while farther to the east, where the unit is thicker and deeper, the calcium sulphate phase is still anhydrite.

    Fluctuations in the watertable level tied to heavy rain or long drought are thought to be the most common triggering mechanism for subsidence transitioning to sinkhole collapse. Many of the more catastrophic collapses occur after river flooding and periods of prolonged rain, which tend to wash away cavern roof span support. Subsidence is also aggravated by groundwater pumping; first, it lowers the watertable and second, it induces considerable crossflow of water in enlarged joints in the gypsum. When recharged by a later flood, the replacement water is undersaturated with respect to gypsum.

    Thomson et al. (1996) recognised four hydrogeological flow units driving karst collapse in the Ripon area (Figure 4):

    1) Quaternary gravels in the buried valley of the proto-River Ure

    2) Sherwood Sandstone Group

    3) Magnesian Limestone of the Brotherton Fm. and the overlying/adjacent gypsum of the Roxby Fm.

    4) Magnesian limestone of the Cadeby Fm. plus the overlying/adjacent gypsum of the Edlington Fm.

    Local hydrological base level within this stratigraphy is controlled by the River Ure, especially where the buried Pleistocene valley (proto-Ure) is filled by permeable sands and gravels, as these unconsolidated sediments, when located atop a breached roof beam, are susceptible to catastrophic stoping to base level (Figure 4). In the area around Ripon the palaeovalley cuts down more than 30 m, reaching levels well into the Cadeby Formation, so providing the seepage connections or pathways between waters in all four units wherever they intersect the palaeovalley. There is considerable groundwater outflow along this route with artesian sulphate-rich springs issuing from Permian strata in contact with Quaternary gravels of the buried valley (Cooper, 1986, 1995, 1998).

    The potentiometric head comes from precipitation falling on the high ground of the Cadeby formation to the west and the Sherwood Sandstone to the east. Groundwater becomes largely confined beneath glacial till as it seeps toward the Ure Valley depression, but ultimately finds an exit into the modern river via the deeply incised sand and gravel-filled palaeovalley of the proto-Ure. Waters recharging the Ure depression pass through and enlarge joints and caverns in the gypsum units of the Edlington and Roxby Formations, so the highest density of subsidence features are found atop the sides of the palaeovalley. This region has the greatest volume of artesian discharge from aquifers immediately beneath the dissolving gypsum bed. Although created as an active karst valley, the apparent density of subsidence hollows is lower on the present Ure River floodplain than the surrounding lands as floodplain depressions are constantly filled by overbank sediments (Figure 4b).

    Cooper (1998) defined 16 sinkhole variations in the gypsum subsidence belt at Ripon, all are types of entrenched, subjacent and mantled karst. Changes in karst style are caused by; the type of gypsum, the nature and thickness of the overlying deposits, presence or absence of consolidated layers overlying the gypsum and the size of voids/caverns within the gypsum.

    To the west of Ripon, the gypsum of the Edlington Formation lies directly beneath glacial drift. These unconsolidated drift deposits and the loose residual marl atop the dissolving gypsum gradually subside into a pinnacle or suffusion (mantled) karst. But between Ripon town and the River Ure, the limestone of the Brotherton Formation overlies the Edlington Formation. There the karst develops as large open caverns beneath strong roof spans (entrenched karst). Ultimate collapse of the roof span creates rapid upward-stoping caverns in loosely consolidated sediment. Stopes break though to the surface as steep-sided collapse dolines or chimneys with sometimes catastrophic results. A similar entrenched situation is found east of the Ure River but there karstified gypsum units of both the Edlington and the Roxby formations are involved.

    There are also thick beds of gypsum in the Permian Zechstein sequence that forms the bedrock in the Darlington area. In this area, subsidence features attributed to gypsum dissolution are typically broad shallow depressions up to 100 m in diameter, and the ponds, known as Hell Kettles, are the only recognized examples of steep-sided subsidence hollows around Darlington (Figure 5). Historical records suggest that one of the ponds formed in dramatic fashion in AD 1179 (Cooper 1995). The southern pond appears to be the most likely one to have formed at that time because it is many metres deep and is fed from below by calcareous spring water that is rich in both carbonate and sulphate. The 2D profiles have revealed evidence of foundering in the limestone of the Seaham Formation at depths of c. 50 m (Figure 5; Sargent and Goulty, 2009). The foundering is interpreted to have resulted from dissolution of gypsum in the Hartlepool Anhydrite Formation at ≈ 70 m depth. The reflection images of the gypsum itself are discontinuous, suggesting that its top surface has karstic topography. The 3D survey also acquired and interpreted by Sargent and Goulty (2009) reveals subcircular hollows in the Seaham Formation up to 20 m across, which are again attributed to foundering caused by gypsum dissolution.

    Problems with Miocene gypsum, Spain

    Karstification has led to problems in areas of subcropping Miocene gypsum in the Ebro and Calatayud basins, northern Spain (Figure 6). Cliff sections and road cuts indicate the widespread nature of karstification in the gypsum outcrops and subcrops in Spain (Figure 7b) Areas affected are defined by subsidence or collapse in Quaternary alluvial overburden and include; urban areas, communication routes, roads, railways, irrigation channels and agricultural fields (Figure 7a; Soriano and Simon, 1995; Elorza and Santolalla, 1998; Guerrero et al., 2013; Gutiérrez et al., 2014). In the region there can be a reciprocal interaction between anthropic activities and sinkhole generation, whereby the ground disturbance engendered by human activity accelerates, enlarges and triggers the creation of new sinkholes. Subsidence is particularly harmful to linear constructions and buildings and numerous roads, motorways and railways have been damaged (Figure 7a, b). Catastrophic collapse and rapid karst chimneying into roads and buildings can have potentially fatal consequences. For example, several buildings have been damaged around the towns of Casetas and Utebo. In the Portazgo industrial estate some factories had to be pulled down due to collapse-induced instability (Castañeda et al., 2009). A nearby gas explosion was attributed to the breakage of a gas pipe caused by subsidence. The local water supply is also disrupted by subsidence and pipe breakage so that 20,000 inhabitants periodically lose their water supply. The most striking example of subsidence affecting development comes from the village of Puilatos, in the Gallego Valley. In the 1970's this town was severely damaged by subsidence and abandoned before it could be occupied (Cooper 1996).

    Collapse affects irrigation channels in the countryside with substantial economic losses (Elorza and Santolalla, 1998). In 1996 a doline collapse surfaced and cut the important Canal Imperial at Gallur village. New dolines often form near unlined irrigation canals. The ongoing supply of fresh irrigation waters to field crops can also encourage sinkhole generation in the fields. Though not directly visible, natural sinkholes also form in the submerged beds of river channels cutting regions of subcropping gypsum.

    On December 19th, 1971, a bus fell from a bridge into the Ebro River at Zaragoza, near where the ‘San Lazaro well’ (a submerged gypsum sinkhole) is located (Figure 8a). Ten people lost their lives in this accident , while the remainder of the passengers were rescued, after being stranded on the bus roof in the flowing river for some hours (Figure 8b). After survivors were rescued, river waters washed the bus from the foot of the bridge supports into the nearby 'San Lazaro well (collapse sinkhole) in the water-covered floor of the river. Nine of the ten bodies in the bus were never found, although the bus was later recovered from the sinkhole. Locals suggested that bodies were carried deeper into the various interconnect phreatic sinkhole caverns fed by this losing stream.

    Karstification in the Zaragoza region is characterised by the preferential intrastatal dissolution of glauberite bed, which are more soluble than the gypsum interbeds, this leads to collapse and rotation of gypsum blocks and river capture (Guerrero et al., 2013).

    Sometimes even well-intentioned attempts to remediate culturally significant buildings under threat of evaporite karst collapse can exacerbate collapse problems. Gutiérrez and Cooper (2002) cite examples from the city of Calatayud, Spain. Subsidence-induced differential loading across doline edges drives the tilting of the 25-metre high tower (mudéjar) of the San Pedro de Los Francos church, which leans towards and overhangs the street by about 1.5 metres. (Figure 9) In places, the brickwork of the church indents the pre-existing tower fabric, which probably dates from the 11th Century or the beginning of the 12th Century. This indentation and the non-alignment of the church and the tower walls indicates that most of the tower tilting occurred prior to the construction of the church. In 1840, the upper 5m of the tower was removed and the lower part buttressed for the safety of the Royal family, who visited the town and stayed in the palace opposite. On 3rd June 1931, San Pedro de Los Francos church was declared a “Monument of Historical and Artistic value.” Due to its ruinous condition, the church was closed to worship in 1979. Micropiling to improve the foundation was started in 1994, but this corrective measure was interrupted when only half of the building was underpinned. Very rapid differential settlement of the building took place in the following year, causing extensive damage and aggravating the subsidence problem.

    Colegiata de Santa María la Mayor was constructed between the 13th and 18th centuries, it has an outstanding Mudéjar (a 72 m high tower) and numerous Renaissance features; it is considered the foremost monument in the city of Cataluyud. As with the San Pedro de los Francos Church, recent micropiling work, applied to only one part of the cloister, has been followed by alarming differential movements that have drastically accelerated the deterioration of the building. Large blocks have fallen from the vault of the “Capitular Hall” and cracks up to 150 mm wide have opened in the brickwork of the back (NW) elevation, which has now been shored up for safety. The dated plaster tell-tales placed in these cracks to monitor the displacement demonstrate the high speed of the deformation produced by subsidence in recent years. On the afternoon of 10 September 1996, the fracture of a water supply pipe flooded the cloisters and the church with 100 mm of muddy water. Ten years earlier a similar breakage and flood had occurred. These breaks in the water pipes are most likely related to karst-induced subsidence. Once they occur, the massive input of water to the subsurface may trigger further destruction via enhanced dissolution, piping and hydrocollapse (Gutiérrez and Cooper, 2002).

    Gypsum karst in Mosul, Iraq

    A similar quandary of multiple areas of structural damage from gypsum-induced subsidence affects large parts or the historic section of the city of Mosul in northern Iraq (Jassim et al., 1997). The main part of its old quarter is over a century old and some buildings are a few hundred years old. Mosul lies on the northeastern flank of the Abu Saif anticline and near to its northern plunge (Figure 10a). It was built on the western bank of the Tigris River on a dip slope of Middle Miocene Fatha limestone that is directly underlain by bedded gypsum and green marl (equivalent to Lower Fars Formation). Houses in the old city were built on what seemed to be at the time a very sound rock foundation.

    Water distribution in the city was done on mule back in the early part of last century and the estimated water consumption did not exceed 10 litres per person per day (Jassim et al., 1997). Discharge from households was partly to surface drainage and partly to shallow and small septic tanks. The modern piped system of water distribution did not start until the 1940s, resulting in a sudden increase in water consumption (presently around 200 litres per person per day) and it was not associated with a complementary sewer system. Increased water consumption meant larger and deeper septic tanks were dug at the perimeter of buildings (which never seemed to fill) resulting in a dramatic increase in water percolating downwards, water that was also more corrosive than previously due to the increased use of detergents and chlorination. This water passes through the permeable and fractured limestone to the underlying gypsum. On its way through the limestone it enlarges and creates new dissolution cavities, but eventually finds its way into the older gypsum karst maze, which is then further widened as water drains back into the Tigris (Figure 10b). Caverns in the gypsum enlarge until the roof span collapses. Since the 1970s more and more buildings in the old city have fractured and many are subject to sudden collapse. The problem is further intensified due to the expansion of the city in the up-dip direction (west and southwest) including the construction of industrial, water-dependent centres with integrated drainage. Water seeping/draining from these newly developed up-dip areas eventually passes under the old city before discharging in the Tigris river. The process was slightly arrested in the 1980s by the completion of a drainage system for the city, but the degradation of the old city continues.

    Coping: man-made structures atop salts

    The towns of Ripon in the UK and Pasvales and Birzai in Lithuania house some 45,000 people, who currently live under the ongoing threat of catastrophic subsidence, caused by natural gypsum dissolution (Paukstys et al., 1999). Special measures for construction of houses, roads, bridges and railways are needed in these areas and should include: incorporating several layers of high tensile heavy duty reinforced plastic mesh geotextile into road embankments and car parks; using sacrificial supports on bridges so that the loss of support of any one upright will not cause the deck to collapse; extending the foundations of bridge piers laterally to an amount that could span the normal size of collapses; and using ground monitoring systems to predict areas of imminent collapse (Cooper 1995, 1998).

    Dams to store urban water supplies are costly structures and failure can lead to disaster, large scale mortality and financial liability (for example, Cooper and Gutiérrez, 2013). For example, at two and a half minutes before midnight on March 12, 1928, the St. Francis Dam (California) failed catastrophically and the resulting flood killed more than 400 people (Figure 11). The collapse of the St. Francis Dam is considered to be one of the worst American civil engineering disasters of the 20th century and remains the second-greatest loss of life in California’s history, after the 1906 San Francisco earthquake and fire. The collapse was partly attributed to dissolution of gypsum veins beneath the dam foundations. The Quail Creek Dam, Utah, constructed in 1984 failed in 1989, the underlying cause being an unappreciated existence of, and consequent enlargement of, cavities in the gypsum strata beneath its foundations.

    Unexpected water leakage from reservoirs, via ponors, sinkholes and karst conduits, leads to costly inefficiency, or even project abandonment. Unnaturally high hydraulic gradients, induced by newly impounded water, may flush out of the sediment that previously blocked karst conduits. It can also produce rapid dissolutional enlargement of discontinuities, which can quickly reach break-through dimensions with turbulent flow. These processes may significantly increase the hydraulic permeability in the region of the dam foundation, on an engineering time scale.

    Accordingly, numerous dams in regions of the USA underlain by shallow evaporites either have gypsum karst problems, or have encountered gypsum-related difficulties during construction (Johnson, 2008). Examples include; the San Fernando, Dry Canyon, Buena Vista, Olive Hills and Castaic dams in California; the Hondo, Macmillan and Avalon dams in New Mexico; Sandford Dam in Texas; Red Rock Dam in Iowa; Fontanelle Dam in Oklahoma; Horsetooth Dam and Carter Dam in Colorado and the Moses Saunders Tower Dam in New York State. Up to 13,000 tonnes of mainly gypsum and anhydrite were dissolved from beneath a dam in Iraq in only six months causing concerns about the dam stability (Figure 13). In China, leaking dams and reservoirs on gypsum include the Huoshipo Dam and others in the same area. The Bratsk Dam in eastern Siberia is leaking, and in Tajikistan the dam for the Nizhne-Kafirnigansk hydroelectric scheme was designed to cope with active gypsum dissolution occurring below the grout curtain. Gypsum karst in the foundation trenches of the Casa de Piedra Dam, Argentina and El Isiro Dam in Venezuela, caused difficult construction conditions and required design modifications.

    Another illustration of the problems associated with water retaining structures and the ineptitude, or lack of oversight, by some city planners comes from the town of Spearfish, South Dakota (Davis and Rahn, 1997 ). As discussed earlier in this chapter, the Triassic Spearfish Formation contains numerous gypsum beds in which evaporite-focused karst landforms are widely documented across its extent in the Black Hills of South Dakota (Figure 12). The evaporite karst in the Spearfish Fm. has caused severe engineering problems for foundations and water retention facilities, including wastewater stabilization sites. One dramatic example of problems in water retention atop gypsum karst comes from the construction in the 1970s of now-abandoned sewage lagoons for the City of Spearfish.

    Despite warnings from local ranchers, the Spearfish sewage lagoons were built in 1972 by city authorities on alluvium atop thick gypsum layers of Spearfish Formation. Ironically, at one point during lagoon construction, a scraper became stuck in a sinkhole and required four bulldozers to pull it out. Once filled with sewage, within a year the lagoons started leaking badly; the southern lagoon was abandoned after four years because of ongoing uncontrollable leaks, and the northern lagoon did not completely drain, but could not provide adequate retention time for effective sewage treatment. Attempts at repairs, including a bentonite liner, were ineffective, and poorly treated sewage discharged beneath the lagoon’s berm into a nearby surface drainage. The lagoons were abandoned completely in 1980. This was after a US $27-million lawsuit was filled in 1979 by ranchers whose land and homes were affected by leaking wastewater. A mechanical wastewater treatment plant was constructed nearby on an outcrop of the non-evaporitic Sundance Formation. The engineering firm that designed the facility without completing a knowledgeable geological site survey was reorganised following the lawsuit.

    Likewise, the development of Chamshir Dam atop Gascharan Formation outcrop and subcrop in Iran is likely to create ongoing infrastructure cost and water storage problems (Torabi-Kaveh et al., 2012). The site is located in southwest of Iran, on Zuhreh River, 20 km southeast of Gachsaran city. The area is partially covered by evaporite formations of the Fars Group, especially the Gachsaran Formation. The dam axis is located on limestone beds of Mishan Formation, but nearly two-thirds of the dam reservoir is in direct contact with the evaporitic Gachsaran Formation. Strata in the vicinity of the reservoir and dam site have been brecciated and intersected by several faults, such as the Dezh Soleyman thrust and the Chamshir fault zone, which all act in concert to create karst entryways, including local zones of suffusion karst. A wide variety of karstic features typify the region surrounding the dam site and include; karrens, dissolution dolines, karstic springs and cavities. These karst features will compromise the ability of Chamshir Dam to store water, and possibly even cause breaching of the dam, via solution channels and cavities which could allow significant water flow downstream of the dam reservoir. As possible and likely partial short term solutions, Torabi-Kaveh et al. (2012) recommend the construction of a cutoff wall and/or a clay blanket floor to the reservoir

    Difficulties in building hydraulic structures on soluble rocks are many, and dealing with them greatly increases project and maintenance costs. Gypsum dissolution at the Hessigheim Dam on the River Neckar in Germany has caused settlement problems in sinkholes nearby. Site investigation showed cavities up to several meters high and remedial grouting from 1986 to 1994 used 10,600 tonnes of cement. The expected life of the dam is only 30-40 years, with continuing grouting required to keep it serviceable.

    Grouting costs in zones of evaporite karst can be very high and may approach 15 or 20% of the dam cost, currently reaching US$ 100 million in some cases. In karstified limestones grouting is difficult, yet in gypsum it is even more difficult due to the rapid dissolution rate of the gypsum. Karst expansion in limestone occurs on the scale of hundreds of years, in gypsum it can be on the order of a decade or less. Grouting may also alter the underground flow routes, so translating and focusing the problems to other nearby areas. In the Perm area of Russia, gypsum karst beneath the Karm hydroelectric power station dam has perhaps been successfully grouted, a least in the short term, using an oxaloaluminosilicate gel that hardens the grout, but also coats the gypsum, so slowing its dissolution. The Mont Cenis Dam, in the French Alps, is not itself affected by the dissolution of gypsum. However, the reservoir storage zone is leaking and photogrammetric study of the reservoir slopes showed ongoing doline activity over gypsum and subsidence in the adjacent land.

    Probably the worst example tied to and evaporite karst hazard is the significant dam disaster waiting to happen that is the Mosul Dam in Iraq (Figure 13; Kelley et al., 2007; Sissakian and Knutsson, 2014; Milillo et al., 2016). It is ranked as the fourth largest dam in the Middle East, as measured by reserve capacity, capturing snowmelt from Turkey, some 70 miles (110 km) north. Built under the despotic regime of Saddam Hussein, completed in 1984 the Mosul Dam (formerly known as Saddam Dam) is located on the Tigris river, some 50 km NW of Mosul.

    The design of the dam was done by a consortium of European consultants (Sissakian and Knutsson, 2014), namely, Swiss Consultants group, comprising: Motor Columbus; Electrowatt; Suiselectra; Societe Generale pour l’Industrie. The construction was carried out by a German-Italian consortium of international contractors, GIMOD joint venture, comprising: Hochtief; Impregilo; Zublin; Tropp; Italstrade; Cogefar. The consultants for project design and construction supervision comprised a joint venture of the above listed Swiss Consultants Group and Energo-Projekt of Yugoslavia, known as MODACON.

    As originally constructed the dam is 113 m in height, 3.4 km in length, 10 m wide in its crest and has a storage capacity of 11.1 billion cubic meters (Figure 13b). It is an earth fill dam, constructed on evaporitic bedrock atop a karstified high created by an evaporite cored anticline in the Fat’ha Formation, which consists of gypsum beds alternating with marl and limestone (Figure 13a, 14). To the south, this is same formation with the same evaporite cored anticlinal association that created all the stability problems in the city of Mosul (Figures 10). The inappropriate nature of the Fat’ha Formation as a foundation for any significant engineering structure had been known for more than a half a century. Then again, absolute rulers do not need to heed scientific advice or knowledge. Or perhaps he didn’t get it from a well-paid group of Swiss-based engineering consultants. As Kelley et al. (2007) put it so succinctly....“The site was chosen for reasons other than geologic or engineering merit.”

    The likely catastrophic failure of Mosul Dam will drive the following scenario (Sissakian and Knutsson, 2014); “... (dam) failure would produce a flood wave crest about 20 m deep in the City of Mosul. It is estimated that the leading edge of the failure flood wave would arrive in Mosul about 3 hours after failure of the dam, and the crest of the flood wave would arrive in Mosul about 9 hours after failure of the dam. The total population of the City of Mosul is about 3 million, and it is estimated that about 2 million people are in locations within the city that would be inundated by a 20 m deep flood wave. The City of Baghdad is located about 350 km downstream of Mosul Dam, and the dam failure flood wave will arrive after 72 hours in Baghdad and (by then) would be about 4 m deep.”

    The heavily karsted Fat’ha Formation is up to 352 m thick at the dam and has an upper and lower member. The lower member is dominated by carbonate in its lower part (locally called “chalky series”) and is in turn underlain by an anhydrite bed known as the GBo. Gypsum beds typify its upper part,and the evaporite interval is capped by a limestone marker bed. The upper member, crops out as green and red claystone with gypsum relicts, around the Butmah Anticline. Thickness of individual gypsum beds below the dam foundations can attain 18 m; these upper member units are intensely karstified, even in foundation rocks, with cavities meters across documented during construction of the dam (Figure 14). Gypsum breccia layers are widespread within the Fatha Formation and have proven to be the most problematic rocks in the dam’s foundation zone. The main breccia body contains fragments or clasts of limestone, dolomite, or larger pieces of insoluble rocks of collapsed material. The upper portion of the accumulation grades upward from rubble to crackle mosaic breccia and then a virtually unaffected competent overburden. Breccia also may form without the intermediate step of an open cavity, by partial dissolution and direct formation of rubble. As groundwater moves through the rubble, soluble minerals are carried away, leaving insoluble residues of chert fragments, quartz grains, silt, and clay in a mineral matrix. These processes result in geologic layers with lateral and vertical heterogeneity on scales of micro-meters to meters.

    High permeability zones in actively karsting gypsum regions can form rapidly, days to weeks, and quickly become transtratal. So predicting or controlling breakout zones via grouting and infill can be problematic (Kelley et al., 2007; Sissakian and Knutsson, 2014). For example, four sinkholes formed between 1992 and 1998 approximately 800 m downstream in the maintenance area of the dam (Figure 13a). The sinkholes appeared in a linear arrangement, approximately parallel to the dam axis. Another large sinkhole developed in February 2003, east of the emergency spillway when the pool elevation was at 325 m. The Mosul Dam staff filled the sinkhole the next day, with 1200 m3 of soil. Another sinkhole developed in July 2005 to the east of the saddle dam. Six borings were completed around the sinkhole and indicated that the sinkhole developed beneath overburden deposits and within layers of the Upper Marl Series. Another cause for concern at Mosul Dam in recent years is a potential slide area reported upstream of the dam on the west bank. The slide is most likely related to the movement of beds of the Chalky Series over the underlying GBo (anhydritic) layer.

    To “cope” with ongoing active karst growth beneath and around the Mosul Dam, a continuous grouting programme was planned, even during dam construction, and continues today, on a six days per week basis. It pumps tens of thousands of tons of concrete into expanding karst features each year (Sissakian and Knutsson, 2014; Milillo et al., 2016). The dam was completed in June 1984, with a postulated operational life of 80 years. Due to insufficient grouting and sealing in and below the dam foundation, numerous karst features, as noted above, continue to enlarge in size and quantity, so causing serious problems for the ongoing stability of the dam. The increase in hydraulic gradient created by a wall of water behind the dam has accelerated the rate of karstification in the past 40 years.

    Since the late 1980s, the status of the dam and its projected collapse sometime within the next few decades has created ongoing nervousness for the people of Mosul city and near surroundings. All reports on the dam since the mid 1980s have underlined the need for ongoing grouting and monitoring and effective planning of the broadcasting of a situation where collapse is imminent. For “Saddam’s dam” the question is not if, but when, the dam will collapse. To alleviate the effects of the dam collapse, Iraqi authorities have started to build another “Badush Dam” south of Mosul Dam so that it can stop or reduce the effects of the first flood wave. However this new dam has a projected cost in excess of US$ ten billion and so lies beyond the financial reach of the current Iraqi government. Problems related to the dam increased with the takeover of the region by the forces of ISIL.

    Today, the Mosul dam is subsiding at a linear rate of ~15 mm/year compared to 12.5 mm/year subsidence rate in 2004–2010 (Milillo et al., 2016). Increased subsidence restarted at the end of 2013 after re-grouting operations slowed and at times stopped. The causes of the observed linear subsidence process of the dam wall can be found in the human activities that have promoted the evaporite–subsidence development, primarily in gypsum deposits and may enable, in case of continuous regrouting stop, unsaturated water to flow through or against evaporites deposits, allowing the development of small to large dissolution cavities.

    Large vertical movements that typified the dam wall have resulted from the dissolution of extensive gypsum strata previously mapped beneath the Mosul dam. Increased subsidence rate over the past five years has been due to periods when there was little or no regrouting underlying the dam basement. Dam subsidence currently seems to follow a linear behavior but on can not exclude a future acceleration due to increased gypsum dissolution speed and associated catastrophic collapse of the dam (Milillo et al., 2016).

    Given the existing geologic knowledge base in the 1980s, in my opinion, one must question the seeming lack of understanding in a group of well-paid consultant engineering firms as to the outcome of building such a major structure, atop what was known to be an active karstifying gypsum succession, sited in a location where failure will threaten multimillion populations in the downstream cities. The same formation that constituted the base to the Mosul dam was known at the time to be associated with ground stability problems atop similar gypsum-cored anticlines in the city of Mosul to the south. Even more concerning to the project rationale should have been the large karst cavities in highly soluble gypsum that were encountered a number of times during feasibility and construction of the dam foundations (Figure 14). Or, perhaps, as Lao Tzu observed many centuries ago, “ ...So the unwanting soul sees what’s hidden, and the ever-wanting soul sees only what it wants.”

    Canals, like dams, that leak in gypsum karst areas can trigger subsidence, which can be severe enough to cause retainment failure. In Spain, the Imperial Canal in the Ebro valley, and several canals in the Cinca and Noguera Ribagorzana valleys, which irrigate parts of the Ebro basin, have on numerous occasions failed in this way. Similarly, canals in Syria have suffered from gypsum dissolution and collapse of soils into karstic cavities. Canals excavated in such ground may also alter the local groundwater flow (equivalent to losing streams) and so accelerate internal erosion, or the dissolution processes and associated collapse of cover materials. In the Lesina Lagoon, Italy, a canal was excavated to improve the water exchange between the sea and the lagoon. It was cut through loose sandy deposits and highly cavernous gypsum bedrock, but this created a new base level, so distorting the local groundwater flow. The canal has caused the rapid downward migration of the cover material into pre-existing groundwater conduits, producing a large number of sinkholes that now threaten an adjacent residential area.

    Pipelines constructed across karst areas are potential pollution sources and some may pose possible explosion hazards. The utilization of geomorphological maps depicting the karst and subsidence features allied with GIS and karst databases help with the grouting and management of these structures. In some circumstances below-ground leakage {Zechner, 2011 #26} from water supply pipelines can trigger severe karstic collapse events. Where such hazards are identified, such as where a major oil and gas pipeline crosses the Sivas gypsum karst in Turkey, the maximum size of an anticipated collapse can be determined and the pipeline strength increased to cope with the possible problems.

    Solving the problem?

    Throughout the world, be it in the US, Canada, the UK, Spain, eastern Europe, or the Middle East, it is a fact that weathering of shallow gypsum forms rapidly expanding and stoping caverns, especially in areas of high water crossflow, unsupported roof beams, and unconsolidated overburden and in areas of artificially confined fresh water. Rapid karst formative processes and mechanism will always be commonplace and widespread (Table 2). Resultant karst-associated problems can be both natural and anthropogenically induced or enhanced. It is fact that natural solution in regions of subcropping evaporites is always rapid, and even more so in areas where it is encouraged by human activities, especially increased cycling of water via damming, groundwater pumping, burst pipes, septic systems, agricultural enhancement and uncontrolled storm and waste water runoffs to aquifers.

    Typically, the best way to deal with a region of an evaporite karst hazard is to map the regional extent of the shallow evaporite solution front and avoid it (Table 3). In established areas with a karst problem the engineering solutions will need to be designed around hazards that will typically be characterised by short-term onsets, often tied to rapid ground stoping/subsidence events and quickly followed by ground collapse. If man-made buildings of historical significance are to be restored and stabilized in such settings, perhaps it is better to wait until funds are sufficient to complete the job rather than attempt partial stabilization of the worst-affected portions of the feature. Significant infrastructure (including roads, canals and dams) should be designed to avoid such areas when possible or engineered to cope with and/or survive episodes of ground collapse.

    A piecemeal approach to dealing with evaporite karst can intensify and focus water crossflows rather than alleviate them. In the words of Nobel prizewinner, Shimon Peres; “If a problem has no solution, it may not be a problem, but a fact - not to be solved, but to be coped with over time.”


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